WO2021242267A1 - Dispositif électrochrome basé sur deux couches colorées et procédés de fabrication de celui-ci - Google Patents

Dispositif électrochrome basé sur deux couches colorées et procédés de fabrication de celui-ci Download PDF

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Publication number
WO2021242267A1
WO2021242267A1 PCT/US2020/035407 US2020035407W WO2021242267A1 WO 2021242267 A1 WO2021242267 A1 WO 2021242267A1 US 2020035407 W US2020035407 W US 2020035407W WO 2021242267 A1 WO2021242267 A1 WO 2021242267A1
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Prior art keywords
color layer
electrochromic device
color
pigmentary
electrochromic
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PCT/US2020/035407
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English (en)
Inventor
Ke Chen
Jianguo Mei
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Ambilight Inc.
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Priority to KR1020227033314A priority Critical patent/KR20230017162A/ko
Priority to EP20937201.0A priority patent/EP4078280A4/fr
Priority to JP2022552940A priority patent/JP2023531349A/ja
Priority to PCT/US2020/035407 priority patent/WO2021242267A1/fr
Priority to CN202080076632.XA priority patent/CN114787707B/zh
Priority to US16/999,921 priority patent/US10955717B1/en
Publication of WO2021242267A1 publication Critical patent/WO2021242267A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F1/15165—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • G02F2001/1536—Constructional details structural features not otherwise provided for additional, e.g. protective, layer inside the cell
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • G02F2001/1557—Side by side arrangements of working and counter electrodes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F2001/164—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect the electrolyte is made of polymers

Definitions

  • the present disclosure is generally related to a new electrochromic device, and more particularly, a new electrochromic device containing a pigmentary color layer and a structural color layer, and also directed to a method for preparing the electrochromic device.
  • Some animals such as cephalopod, fish and butterflies, are able to dynamically change skin coloration states as means of communication, camouflage, predation or regulating body temperature.
  • One kind of organ and one kind of cell are mainly responsible for their color states, namely chromatophore and iridophore respectively.
  • Chromatophores are organs that contain a large amount of pigment cells and are usually mounted on radial muscles. With the expansion and contraction of the muscles, these pigment cells could reversibly spread out or shrink into little invisible spots (0.1 mm in area). This process lends animals to dynamically change gradient transparency or patterns on demand.
  • Iridophores are stacks of very thin cells which give rise to structural colors, resulting from reflection of light at the specific wavelengths by their nanocrystals.
  • the nanocrystals polarize light and cause angle dependent color which enable animals to hide from predators.
  • These two organs are lying adjacently underneath skin and function synergistically, which offers color tunability that neither of them can achieve alone, such as expressing broaden color gamut, transparency, and angle-dependent visibility.
  • Such a cooperative interaction enables animals exhibit impressive color adaptability to their surrounding environments.
  • the disclosure describes an electrochromic device comprising a pigmentary color layer and a structural color layer.
  • the pigmentary color layer comprises the pigmentary color materials which produce colors by the light absorption
  • the structural color layer comprises the structural color materials which produce colors by the physical interaction of periodic structures with light, such as reflection and refraction.
  • the structural color layer comprises a structural color material which has an angle-dependent light variation. Both color layers are placed along the optical path.
  • the top color layer along the optical path has a transmittance and a thickness which allow the disclosed electrochromic device to produce noticeable angle-dependent light variations for corresponding applications.
  • the noticeable angle-dependent light variations may include variations on different colors or different light intensities or both.
  • the metastable colloidal crystals based structural color layer is disposed on the top of electrochromic conjugated polymer (ECP) based pigmentary color layer along the optical path in the example electrochromic device.
  • ECP electrochromic conjugated polymer
  • the structural color layer has a thickness of around 1mm and a transmittance of at least 75% across the majority of UV-vis range at an amorphous domain.
  • the pigmentary color layer and the structural color layer can be placed either directly adjacently or spaced by other compartments. At least the pigmentary color layers comprise electrochromic materials and the electrochromic materials are placed in a closed electric circuit within the electrochromic device. In some embodiments, all the other compartments on top of the structural color layer along the optical path are transparent. This coupling between two color layers enables the disclosed electrochromic device to reversibly switch between saturated colored state and optical transparence by applying an electric voltage. It also broadens the color gamut and boost the color expression capability which neither can achieve alone. Further the disclosed electrochromic device exhibits angle-dependent light variation: the color blueshift with increasing view angle and is only visible from certain angles at specific voltages.
  • the structural color layers are placed on top of the pigmentary color layers along the optical path.
  • the pigmentary color layers are placed on the top along the optical path.
  • the top color layer has a transmittance and a thicknesses, so that the electrochromic devices of the disclosure can produce noticeable angle-dependent light intensity variations for corresponding applications.
  • the two color layers can be placed either directly adjacently or spaced by other compartments.
  • the pigmentary color layer comprises electrochromic materials while the structural color layer contains no electrochromic materials
  • both pigmentary color layer and structural color layer comprise electrochromic materials.
  • the electrochromic materials can be selected from both inorganic materials and organic materials.
  • electrochromic conjugated polymers ECPs
  • ECPs electrochromic conjugated polymers
  • ProDOT acrylate-substituted propylenedioxythiophene
  • Various embodiments described herein are directed to structure designs for assembling the electrochromic devices in the present disclosure.
  • the structure designs described herein comprise two color layers.
  • the two color layers can be placed directly adjacently.
  • sandwich structure designs with two color layers sandwiched between electrodes are used; in some embodiments, lateral structure designs with two color layers placed laterally between two laterally arranged electrodes are used.
  • liquid cell structure designs are used with liquid electrolyte and no greater than one liquid color layer.
  • Two color layers can be also spaced by the other compartments, in another word, while the pigmentary color layer is interposed between two electrodes, the structural color layer is disposed on an outer surface of one of the two electrodes.
  • the structural color materials can be directly coated on an existing ECD.
  • At least pigmentary color layer has electrochromic materials.
  • the color layers with electrochromic material are placed in a closed electric circuit in the electrochromic device.
  • Sharable or separated electric circuit can be used for different applications when both color layers comprise electrochromic materials.
  • the structural color layer comprises insulating color materials
  • structural color materials can be embedded into electrolyte to form one consolidated structural color layer; or the structural color materials can be directly coated onto an existing ECD, in another word, while the pigmentary color layer is interposed between two electrodes, the structural color layer is disposed on an outer surface of one of the two electrodes.
  • the structural color layer comprises conducting color materials
  • structural color materials can either be embedded into electrolyte to form one consolidated structural color layer or form an individual layer directly or be directly coated onto an existing ECD.
  • the electrochromic material in the pigmentary color layer is selected from one or more redox-active inorganic or organic based electrochromic materials, or any combination thereof.
  • Example inorganic pigmentary color materials may be selected from one or more oxides of Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Cu, Ce, or Zn or a mixed metal oxide or a doped metal oxide or any combination thereof, among others.
  • Example organic pigmentary color materials may be selected from one or more of viologens including poly(decylviologen) and its derivatives, electrochromic conducting polymers including polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyfurane and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, and copolymers thereof, metallopolymers, metallophthalocyanines, or the copolymers containing acceptor units including benzothiadi azole, benzoselenadiazole, benzooxazole, benzotri azole, benzoimidazole, quinoxalines, or diketopyrrolopyrroles, or any combination thereof, among others.
  • viologens including poly(decylviologen) and its derivatives
  • electrochromic conducting polymers including poly
  • the pigmentary color layer comprises an electrochromic conjugated polymer (ECP) that can be switched between colored state and bleached state by electric field.
  • ECP electrochromic conjugated polymer
  • the pigmentary color layer comprises acrylate-substituted propylenedioxythiophene (ProDOT) polymers with various colors, for example ECP -black which yields black color.
  • ProDOT propylenedioxythiophene
  • the structural color layer materials can be selected from one or more structural color materials.
  • Example materials include materials produced by lithography techniques (for example, magnetic nanoparticles), liquid crystals (for example, cholesteryl benzoate and its derivate, phospholipids, ZnCE), block copolymers (for example, PS-b-P2VP, PLA-b-PnBA) and colloidal particles (for example, SiCh, ZnO, Ag nanoparticles).
  • the structural color layer materials comprise metastable colloidal crystals which include both crystalline domains and amorphous domains.
  • the amorphous domains need to transmit light to some degree (for example transparent or semi-transparent) to forms unobstructed light pathways for the pigmentary color layer.
  • the crystalline domains give rise to the structure color.
  • the structural color layer comprises SiC /EG (ethyl glycol) non-closed packed colloidal crystals which include both crystalline domains and amorphous domains.
  • the present disclosure is directed to methods of preparing the electrochromic device described immediately above.
  • the method includes preparation of a pigmentary color layer and a structural color layer.
  • At least the pigmentary color layer comprises electrochromic materials and the top color layer has appropriate transmittance and thickness which allow the disclosed electrochromic device to produce noticeable angle-dependent light variations for corresponding applications and the structural color material can be embedded into the electrolyte to form one consolidated structural color layer or be directly coated onto an existing ECD if there is any insulating color material.
  • the final electrochromic device is fabricated with the electrochromic materials placed in a closed electric circuit. Both color layers are placed along the optical path The two color layers can be placed either directly adjacently or spaced by other compartments and all the other compartments on top of the structural color layer along the optical path may be transparent.
  • the methods to make the disclosed electrochromic device include: preparation of a pigmentary color layer comprising a ECP; preparation of a consolidated structural color layer comprising a non-closed packed colloidal crystal embedded in electrolyte; and fabrication of the final device with a sandwich structure design by placing both color layers in a closed electric circuit with transparent substrates, electrodes, an electrolyte layer and an ion storage layer.
  • each layer can be cut and bent into a desired shape before or after assembly, so that the entire device can be fabricated into a desired shape for various applications, including wearable or curved electronic devices.
  • patterned electrodes and substrates can be used to assemble multiplex devices, so the device can be used for high-resolution display and camouflage pattern construction with computational programming.
  • the electrochromic devices in the present disclosure can be used in various applications including, for example, anti-counterfeiting packaging, bills or goods; anti-voyeur screens; logo display, vehicles with camouflage purposes, protective coating of the device to reflect harmful wavelength.
  • FIGS. 1 (A)-(B) are the example working mechanisms of one example electrochromic device (ECD).
  • FIG. 1(A) is a schema diagram illustrating the structure design and the optical path of the described example ECD of the present disclosure with electric actuation (upper) and without electric actuation (lower), according to an example embodiment;
  • FIG. 1(B) is a schema diagram illustrating that the coupled color can be visible from small or zero viewing angles while become invisible from large angles Q during two-stage transition process, according to one example embodiment.
  • FIG. 2 is a diagram illustrating a cross sectional view of an example sandwich structure design of an ECD, according to one example embodiment.
  • FIG. 3 is a diagram illustrating a perspective view of a lateral structure design of an ECD, according to one example embodiment.
  • FIG. 4 is a diagram illustrating an example liquid cell structure design of an ECD, according to one example embodiment.
  • FIGS. 5 (A)-(B) contain the following graphs of an ECP -black used as pigmentary color layer:
  • FIG. 5(A) shows a cyclic voltammogram with images at colored states and bleached states;
  • FIG. 5(B) shows transmittance changes at 550nm when the voltage switches between -1.3 V to 2.7 V, according to some embodiments of the disclosure.
  • FIGS. 6 (A)-(D) contain the following graphs of a metastable colloidal crystal used as structural color layer:
  • FIG. 6(A) is an optical microscope image;
  • FIG. 6(B) illustrates reflectance spectra;
  • FIG. 6(C) is SEM image of the crystal domain of the metastable colloidal crystal;
  • FIG. 6(D) is SEM image of the amorphous domain of the metastable colloidal crystal, according to some embodiments of the disclosure.
  • FIG. 7 is the flow diagram illustrating a fabrication process for forming an electrochromic device in a sandwich structure design, according to one example embodiment.
  • FIGS. 8 (A)-(B) are the spectra for an ECD when the voltage increases from -1.3 V to 2.7 V:
  • FIG. 8(A) is transmittance spectra of ECP -black as pigmentary color;
  • FIG. 8(B) is reflectance spectra of the colloidal crystal as structural color, according to some embodiments of the disclosure.
  • FIGS. 9 (A)-(F) are images of an electrochromic device for illustration of the color changes at different voltages, from left to right, -1.3V, 1.2V, 1.7 V, 2V, 2.4V, and 2.7V, according to one example embodiment.
  • FIGS. 10 (A)-(C) contain the following graphs of the disclosed example electrochromic devices when ECPs are at bleached states, wherein the electrochromic devices comprise green colloidal crystal as the structural color layers and various ECPs as the pigmentary color layers: the spectra of the devices which comprise ECP-magenta (illustrated in FIG. 10(A)) or ECP-green (FIG. 10(B)) or ECP- blue (FIG. 10(C)).
  • FIGS. 11 (A)-(C) contain the following graphs of the disclosed example electrochromic devices when ECPs are at colored states, wherein the electrochromic devices comprise green vivid colloidal crystal as the structural color layers and various ECPs as the pigmentary color layers: the spectra of the devices which comprise ECP-magenta (illustrated in FIG. 11(A)) or ECP-green (FIG. 11(B)) or ECP- blue (FIG. 11(C)).
  • FIGS. 12 (A)-(B) are the corresponding transmittance and reflectance spectra of the example electrochromic device comprising ECP -black at small angle 15 0 (FIG. 12(A)) and large angle 60° (FIG. 12(B)) wherein the black lines represent transmittance while the grey lines represent reflectance.
  • FIGS. 13 (A)-(B) are images showing the coupled color and visibility change at two different viewing angles of a fish-shaped electrochromic device, small viewing angle (FIG. 13(A)) and large viewing angle (FIG. 13(B)), according to one example embodiment.
  • FIGS. 14 (A)-(E) contain the following graphs: transmittance spectra of the disclosed example electrochromic device at incident angles changed from 15° to 75° , according to one example embodiment, at different voltages of -1.3 V (FIG. 14(A)), 1.2V (FIG. 14(B)), 1.8V (FIG. 14(C)), or 2.7V (FIG. 14(D)); and reflectance spectrum (illustrated in FIG. 14(E)) of the same electrochromic device as the incident angles changed from 15 0 to 75 0 and there are no significantly differences on reflectance at different voltages.
  • FIGS. 15 (A)-(I) contains images illustrating the angle-dependent light variation and electric-field tunability of an example electrochromic device, according to one example embodiment.
  • the viewing angles are 0 °, 45 °, 70 0 from left to right, and the applied voltages are -1.3 V, 1.5 V, 2.7 V from top to bottom.
  • FIGS. 16 (A)-(F) contain images illustrating the angle-dependent variation of an example electrochromic device, according to one example embodiment, under high intensity front light (illustrated in FIG. 16(A)-(C)) or under high intensity back light (illustrated in FIG. 16(D)-(F)).
  • the viewing angles are 0 °, 45 °, 70 ° from left to right.
  • FIGS. 17 (A)-(B) are images of an wearable octopus-patterned example electrochromic device mounting on the arm of a toy bear which shows up at neutral state (illustrated in FIG. 17(A)), and hides away (illustrated in FIG. 17(B)) with electric tuning.
  • FIGS. 18 (A)-(C) are images of an butterfly-shaped example electrochromic device placing in flowers, according to one example embodiment. It shows up at neutral state (illustrated in FIG. 18(A)), becomes transparent after being electric actuated (illustrated in FIG. 18(B)), and can become visible again when viewed from another angle under the same electric condition as (illustrated in FIG. 18(C)).
  • FIGS. 19 (A)-(F) contain the following graphs: FIG. 19(A) is a schema diagram illustrating a three-by-three arrays of an example multiplex electrochromic device, according to one example embodiment; FIG. 19(B) is an image of this example multiplex device that can be bent; FIGS. 19(C)-(F) are images of the same example multiplex device before (left) and after (right) being selectively actuated with electric fields.
  • Various embodiments described herein are directed to an electrochromic device (ECD) comprising one pigmentary color layer and one structural color layer, wherein at least the pigmentary color layers comprise electrochromic materials and are placed in a closed electric circuit with other compartments in the device.
  • the top color layer along the optical path has a transmittance and a thickness, which allows the disclosed ECD to display versatile color expression as well as noticeable angle-dependent light variations for corresponding applications.
  • the perceived color displayed by the disclosed device is coupled by two types of color sources: one is the transmitted light through the device and the other one is the reflective light from the device.
  • the transmitted light mainly comes from the light transmitted through pigmentary color layer after its absorption.
  • the reflected light mainly comes from the light which are selectively reflected by the structural color layer.
  • pigmentary color layers comprise electrochromic materials while structural color layers contains no electrochromic materials.
  • both pigmentary color layer and structural color layer comprise electrochromic materials.
  • the working mechanism of the present disclosure is further illustrated by some example embodiments which have pigmentary color layer containing electrochromic materials and placed on the back of the structural color layer along the optical path as the schema in FIG. 1(A).
  • the perceived color detected by naked eyes or detector is the coupled color from two types of light sources: one is the transmitted light from the light from the back of the device transmitted through the pigmentary color layer after its absorption, and the other one is the reflective light from the light reflected by the structural color layer.
  • the pigmentary color layer is activated by electric field and in a bleached state, the transmittance of the pigmental color layer is high over the entire visible range, so the transmittance of the disclosed ECD is high over the entire visible range.
  • the transmitted light from the backward pigmentary color layer travels through the structural color to the front surface of the ECD and couples with the reflected light, as show in upper FIG. 1(B).
  • the reflected light of the structural color layer changes (lower intensity according to one example) and further leads to angle-dependent light variation at the front surface of the ECD as shown in lower FIG. 1(B).
  • the structure designs described herein comprise two color layers.
  • the two color layers can be placed directly adjacently.
  • sandwich structure designs with two color layers sandwiched between electrodes are used; in some embodiments, lateral structure designs with two color layers placed laterally between two laterally arranged electrodes are used.
  • liquid cell structure designs are used with liquid electrolyte and no greater than one liquid color layer.
  • Two color layers can be also spaced by the other compartments.
  • the structural color materials can be directly coated on an existing ECD. At least pigmentary color layer has electrochromic materials. The color layers with electrochromic material are placed in a closed electric circuit in the electrochromic device.
  • Sharable or separated electric circuit can be used for different applications when both color layers comprise electrochromic materials.
  • the structural color layer comprises insulating color materials
  • structural color materials can be embedded into electrolyte to form one consolidated structural color layer or be directly coated on an existing ECD.
  • the structural color layer comprises conducting color materials
  • structural color materials can either be embedded into electrolyte to form one consolidated structural color layer or form an individual layer or be directly coated on an existing ECD.
  • the electrochromic devices of the present disclosure are depicted in a sandwich structure design as shown in FIG. 2, according to one example embodiment.
  • the two color layers are sandwiched between the other compartments of the disclosed electrochromic device
  • the structural color materials can be directly coated on an existing ECD or be embedded in electrolyte to form one consolidated structural color layer when the structural color materials comprise insulating structural color materials.
  • An example electrochromic device of the present disclosure has a consolidated structural color layer embedded in electrolyte as shown in FIG. 2.
  • the example electrochromic device 200 includes a first transparent substrate 206, a first transparent electrode 208 disposed on the first transparent substrate 206, a pigmentary color layer 202 disposed on the first transparent electrode 208, a structural color layer embedded in electrolyte 204 disposed on the pigmentary color layer 202, an ion storage layer 210 disposed on the structural color layer embedded in electrolyte 204, a second transparent electrode 212 disposed on the ion storage layer 210, a second transparent substrate 214 disposed on the second transparent electrode 212, and a power supply 218 connected to the first transparent electrode 208 and the second transparent electrode 212.
  • At least one of the color layers (202 and 204) comprises electrochromic materials and the top color layer along the optical path has a transmittance and a thickness, which allows for noticeable angle-dependent light variation.
  • the optical path go through the two color layers 204, 202 as well as the other compartments 206, 208, 210, 212, and 214 in the disclosed electrochromic device.
  • all the other compartments on top of the structural color layer along the optical path may be transparent.
  • the electrochromic devices of the present disclosure are depicted in a lateral design.
  • the two color layers are placed laterally between two electrodes in the disclosed example electrochromic device.
  • the optical path penetrates the two color layers, electrolyte and the transparent substrates.
  • the optical path do not need to penetrate the two electrodes nor the ion storage layer.
  • the optical path is not in the same planar with the disclosed electrochromic device.
  • the two electrodes and the ion storage layer do not need to be transparent since they can be out of the optical path.
  • a transparent substrate 306 which may be glass, polyethylene terephthalate (PET) or any other suitable materials transparent in the visible or near IR, is provided with two laterally deposited electrodes 308 and 312.
  • the two color layers, structure color layer 304 and pigmentary color layer 302 are coated directly on one of the electrodes 312.
  • Ion storage layer 310 is deposited on the other electrode 308.
  • Electrolyte solution 316 is spread to cover the entire device.
  • the optical path penetrate the two color layers 302 and 304, electrolyte 316, and the transparent substrate 306 in the disclosed electrochromic device.
  • the optical path do not need to penetrate the two electrodes 308 and 312 nor the ion storage layer 310.
  • the electrochromic devices of the present disclosure are depicted in a liquid cell structure design as shown in FIG 4.
  • electrolyte is in a liquid form.
  • the materials for one of the two color layers can be in a liquid form.
  • the liquid cell structure design varies with different physical states of the two color materials.
  • both color materials can be deposited on the working electrodes with the appropriate color materials on the top.
  • the liquid color material can be dissolved in electrolyte while the other non-liquid color material is deposited on the working electrode.
  • FIG. 4 shows an example liquid cell device 400 with liquid pigmentary color material.
  • the liquid pigmentary material 402 dissolved in the liquid electrolyte 416 is poured into a liquid cell 418.
  • the liquid cell device 400 is further sealed for leak free operation.
  • the electrochromic material in the pigmentary color layer is selected from one or more redox-active inorganic or organic based electrochromic materials, or any combination thereof.
  • Example inorganic pigmentary color materials may be selected from one or more oxides of Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Cu, Ce, or Zn or a mixed metal oxide or a doped metal oxide or any combination thereof, among others.
  • Example organic pigmentary color materials may be selected from one or more of viologens including poly(decylviologen) and its derivatives, electrochromic conducting polymers including polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyfurane and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives, and copolymers thereof, metallopolymers, metallophthalocyanines, or the copolymers containing acceptor units including benzothiadi azole, benzoselenadiazole, benzooxazole, benzotri azole, benzoimidazole, quinoxalines, or diketopyrrolopyrroles, or any combination thereof, among others.
  • viologens including poly(decylviologen) and its derivatives
  • electrochromic conducting polymers including poly
  • the structural color materials for structural color layers in the described electrochromic devices of the present disclosure may be selected from a group of materials including, but not limit to, materials produced by lithography techniques (for example, magnetic nanoparticles), liquid crystals (for example, cholesteryl benzoate and its derivate, phospholipids, ZnC12), block copolymers (for example, PS-b-P2VP , PLA-b-PnBA) and colloidal particles (for example, SiC , ZnO, Ag nanoparticles).
  • lithography techniques for example, magnetic nanoparticles
  • liquid crystals for example, cholesteryl benzoate and its derivate, phospholipids, ZnC12
  • block copolymers for example, PS-b-P2VP , PLA-b-PnBA
  • colloidal particles for example, SiC , ZnO, Ag nanoparticles
  • the pigmentary color layers comprise electrochromic polymer (ECP) as electrochromic materials.
  • ECP electrochromic polymer
  • the pigmentary color layer comprises ECP-black, while the structural color layer comprises a non- closed packed SiCh/EG (ethyl glycol) colloidal crystal which present vivid green stmctural color.
  • Electric field can reversibly and quickly regulate the light coming from the underneath pigmentary color layer and thus control the displayed color of the entire device.
  • Angle-dependent light variation can also be achieved. In the middle of colored-bleached transition process, the coupled color can be visible from relatively small or zero viewing angles while invisible from lager angles.
  • both the pigmentary color layer and the structural color layer comprise electrochromic materials.
  • the pigmentary color layer comprises amorphous tungsten oxide, which optical properties can switch between a bleached state and a colored (dark blue) state upon an applied electric field.
  • the structural color layer comprises a semi-transparent polymers (such as polyurethane) with inverse opaline microporous structure.
  • the coupled color can be obtained by layering the polymer on the top of tungsten oxide. Under the actuation of the electric filed, the ions will penetrate into and swell the polymer, which leads to the crystalline distance change and thus color change.
  • the described electrochromic device displays various coupled colors and angle-dependent light variation.
  • the method of preparing a solid or gel-based electrochromic device of present disclosure comprises, forming two thin film color layers with one pigmentary color layer and one structural color layer, sandwiched or laterally deposited between two electrodes with an ion storage layer deposited directly on the counter electrode, adding electrolyte to form a closed electric circuit and fixation of the electrolyte.
  • the two color layer thin film can be placed either directly adjacently or spaced by other compartments.
  • structural color materials can be either embedded in the electrolyte or be directly coated on an existing ECD.
  • the method of preparing a liquid cell electrochromic device of present disclosure varies with different color materials.
  • depositing the two color layers on the working electrode with the top layer has a transmittance and a thickness, which allows the disclosed ECD to display versatile color expression as well as noticeable angle-dependent light variations for corresponding applications, depositing an ion storage layer on the counter electrode, adding electrolyte, and sealing of the device.
  • depositing the two color layers on the working electrode with the top layer has a transmittance and a thickness, which allows the disclosed ECD to display versatile color expression as well as noticeable angle-dependent light variations for corresponding applications, depositing an ion storage layer on the counter electrode, adding electrolyte, and sealing of the device.
  • the method of preparing an electrochromic device of present disclosure involves another existing electrochromic device.
  • Structural color layer can be deposited directly on the existing electrochromic device to form a thin film
  • the depositing processes with solvent dissolvable color materials coated into films can be realized with any one of a variety of conventional solution- compatible coating techniques, including, but not limited to, ink-jet printing, spray coating, spin coating, slot-die coating, slit coating, roll-to-roll coating, transfer coating, and wire bar coating.
  • the pigmentary color layers comprise electrochromic materials, such as electrochromic polymers (ECPs), as the energy storage material that can reversibly and quickly regulate the transmitted light and thus control the transparency of the platform by electric- field tuning.
  • ECPs electrochromic polymers
  • the pigmentary color layer comprises acrylate-substituted propylenedioxythiophene (ProDOT) polymers with various colors, for example ECP-black.
  • ProDOT propylenedioxythiophene
  • ECP-black as pigmentary color layer is placed on the back of the structural color layer along the optical path. Electric field can reversibly and quickly regulate the light coming from the underneath pigmentary color layer and thus control the displayed color of the entire device.
  • Insertions of FIG 5(A) show the images of ECP-black that can reversibly switch between colored states and bleached states as it is oxidized and reduced, also as shown by the transmittance changes at 550nm in FIG. 5(B).
  • the structural color layers comprise non-closed packed SiOi/EG (ethyl glycol) colloidal crystal consisted of 40% monodispersed silica nanoparticles and 60% EG/PEGDA gel matrix which include both crystalline domains and amorphous domains.
  • the optical microscope image in FIG. 6(A) clearly shows the phase separation of crystalline domains, and amorphous domains.
  • the crystalline domains comprise periodically arranged silica nanoparticles and yield vivid green as shown by bright spots with arrow 1, while amorphous domain comprises randomly dispersed nanoparticles, thus displays dark area as shown by arrow 2.
  • FIG. 6(B) shows the reflectance spectra of the metastable colloidal crystal.
  • the crystalline domains give rise to vivid green structure color by high reflectance of nearly single-wavelength light ( ⁇ 530nm) as shown by the solid line, while low reflectance of the amorphous domains, shown by dashed line, form unobstructed light pathway for the underneath pigmentary color layer.
  • SEM images from FIG. 6(C) and FIG. 6(D) demonstrate their structure difference.
  • FIG. 6(C) shows crystal domain as silica nanoparticles self-assembled into crystal structure, while the SEM image from FIG. 6(D) shows the homogenous amorphous gel matrix as non-periodical arrangement of silica nanoparticles dispersed in the EG/PEGDA.
  • the method of preparing a sandwich structure ECD of the present disclosure with ECP-black for pigmentary color layer and a non-closed packed SiCh/EG (ethyl glycol) colloidal crystal for structure color layer comprises multiply steps as shown in FIG. 7.
  • Step 1 is the preparation of a pigmentary color layer 702 with ECP-black on an ITO coated glass
  • step 2 is the preparation of an ion storage layer 710 with M>2q5 on an ITO coated glass
  • step 3- 5 are the preparation steps of structural color layer 704 by forming a colloidal crystal layer embedded in electrolyte
  • step 6 is the final assembling process of the two color layers (702 and 704) and ion storage layer 710 and other compartments.
  • Preparation of pigmentary color layer with ECP-black 702 on an ITO coated glass comprises: dissolving ECP in the chloroform to form 40mg/ml ECP/chloroform solution, followed by spin-coating of the ECP/chloroform solutions on an ITO coated glass with spin speed of 1500 RMP and drying inside an oven at 90° to form an ECP thin film (step 1) with an appropriate thickness which not affects the minimum amount of transmittance when the device is colored.
  • Preparation of an ion storage layer 710 with M12O5 on an ITO coated glass comprises: preparation of M>2q5 thin films using niobium ethoxide solution via the sol-gel reaction on to an ITO coated glass, annealing at 150 °C for 10 min, and removing organic residues by ultraviolet ozone for 20 mins.
  • Preparation of the structural color layer 704 comprises: dispersing S1O2 particles evenly in the mixture of EG (ethylene glycol, 4.5%), PEGMA (polyethylene glycol) methacrylate, 1.5%) and ethanol (94%) at room temperature, removing ethanol in an oven at 90 °C for 2h to form a supersaturated SiCh/EG colloidal solution, placing supersaturated S1O2/EG colloidal solution sandwiched between two pieces of glass with some certain interval (step 3).
  • this phase separation structure is fixed by crosslinking after being shined under commercial UV light for 10 minutes (step 4).
  • patterned devices for example the device with octopus pattern in FIGS. 16 and the device with butterfly pattern shown in FIGS. 17, a hallow patterned sticky photo mask with a special pattern (for example octopus or butterfly) is placed on top of colloidal crystal solution before UV curing.
  • the colloidal solution not covered by the mask then forms a solid gel with some of the S1O2 nanoparticles to participate out to form crystalline domain and some are still evenly dissolved in the solvent as the amorphous domain.
  • the remaining liquid colloidal solution under the covered part of mask is washed away, leaving behind the patterned solid gel.
  • Gel Electrolyte is prepared by mixing PEGDAsoo, 0.2 M LITF I/PC in volume ratio of 1:1 and stirred overnight in a nitrogen-filled glovebox. Sufficient electrolyte is then added and fixed to embed the formed structural color layer with electrolyte (step 5).
  • step 6 The colloidal crystal embedded in electrolyte as structural color layer 704 is then sandwiched between the pigmentary layer 702 deposed on an ITO coated glass formed in step 1 and ion storage layer 710 deposed on another ITO coated glass formed in step 2 to form the final sandwich structure (step 6). Additional electrolyte is added and fixed in step 6 to form a stable and closed electric circuit.
  • the underneath pigmentary color layer comprises ECP-black electrochromic material
  • the structural color layer, on the top of pigmentary color layer along the optical path comprises a non-closed packed S1O2/EG (ethyl glycol) colloidal crystal and no electrochromic material.
  • the pigmentary color layer comprises electrochromic material, ECP- black, which can switch between colored state and bleached state. In colored state of ECP-black with a voltage of -1.3 V, ECP-black has low transmittance over the entire visible range as shown by the lowest transmittance curve in FIG. 8(A), which means very limited light can penetrate the pigmentary color layer.
  • the pigmentary color layer shows the color of ECP- black (for example black in this embodiment), shown by the image of ECP-black at colored state as the lower left insertion of FIG. 5(A).
  • ECP-black gets oxidized and its absorption peak is red shifted which makes it gradually transparent, as shown by the highest transmittance curve in FIG. 8 (A) and the image of ECP-black at bleached state as upper right insertion in FIG. 5(A).
  • the bleached state can again be switched back to colored state by applying a negative bias (-1.3 V) with the reduction of electrochromic polymer, thus the reflection dominates again for the electrochromic device.
  • This change can also be tuned in steps with different voltages, thus to realize a greyscale change, as shown by the color changing images at different voltages from -1.3V to 2.7V in FIG. 9 (A)-(F), according to one example embodiment.
  • ECPs at colored states, ECP -magenta shows purple color, ECP -green shows green color, and ECP-blue shows blue color
  • ECPs at colored states, ECP -magenta shows purple color, ECP -green shows green color, and ECP-blue shows blue color
  • FIGS. 10(A)-(C) when ECPs are at bleached states
  • FIGS 11(A)-(C) when ECPs are at colored state
  • FIG. 10(B) for ECD containing ECP-green
  • FIG. 10(C) for ECD containing ECP-blue.
  • the black lines correspond to transmittance and grey lines correspond to reflectance.
  • Black numbers are the R, G, B values calculated from transmittance spectra of ECD and grey numbers are those values calculated from reflectance spectra of ECD.
  • the corresponding colors of each set of R, G, B values are represented on the right by beam 1 as transmittance of ECD and beam 2 as reflectance of ECD, respectively.
  • the perceptive color blocks on the very right side are predicted by adding R, G, B values from beam 1 and beam 2.
  • FIGS. 11(A)-(C) show, when ECPs are at colored states, combining two kinds of colors can produce more colors which cannot be produced alone by neither electrochromic polymer nor colloidal crystal.
  • spectra detection and color calculations in FIGS. 10(A)-(C) show that the color addition is less affected by adding of colloidal crystal when ECPs are at bleached states. This is because in a bleached state of each polymer, the transmitted white light from underneath ECPs will dominate the eye perception and pales the reflected light from structure color.
  • angle-dependent light variation can also be achieved by the described electrochromic device of the present disclosure.
  • the coupled color can be visible from relatively small or zero viewing angles while invisible from lager angles as show by the schema in FIG. 1(B).
  • the transmittance of ECPs remains the almost same at different incident angles as shown by the black lines in FIG. 12 when applying a voltage of 1.2Y.
  • the colloidal crystal structural color layer shows a higher reflection at low incident angle 15° as the grey line in FIG. 12(A), but shows a lower reflection at high incident angle 60° as the grey line in FIG. 12(B).
  • an example electrochromic device with ECP-black and green colloidal crystal as two color layers is adopted again.
  • the device is applied with voltages of -1.3 V, 1.2V, 1.7 and 2.5V in steps, so that the ECP-black is brought from the colored state to the bleached state gradually.
  • transmittance (FIGS. 14 (A)-(D)) and reflectance (FIG. 14(E)) of the device are detected from 15° to 75 0 in steps of 15°.
  • Various transmittance spectra are detected at various voltages of -1.3 V (A), 1.2V (B), 1.7V (C), and 2.5V (D).
  • FIGS. 14 show that the transmittance increases (from ⁇ 0%- -60%) with the increasing of voltages. Within various viewing angles, the transmittance at the largest viewing angle 75° increase faster than those at other lower viewing angles which are demonstrated by the transmittance curve at 75° goes from the very bottom of the curves at voltage of -1.3 V, 1.2 V, 1.7 V (shown in FIGS. 14 (A)-(C)) to the very top of the curves at voltage of 2.7 V (shown in FIGS. 14 (D)).
  • FIG. 14(E) shows the dramatically reflectance decreasing (from >60% to ⁇ 10%) and shifting to shorter wavelengths with the increase of viewing angles.
  • the angle-dependent light variation of the present disclosure is also demonstrated by images in FIG. 15.
  • the viewing angles are 0 °, 45 °, 70 0 from left to right, and the applied voltages are -1.3 V, 1.5 V, 2.7 V from top to bottom.
  • vivid green color is changed to green-blue and blue when viewing angles change from 0 0 to 45 0 and to 70 “(illustrated in FIGS. 15 (A)-(C)).
  • angle-dependent light variation can be observed as the green-blue color gradually disappeared in FIGS. 15(D)-(F) when the viewing angles increase.
  • the last row with a voltage of 2.7 V, the device becomes transparent and from any angles, while no significant color change could be observed from any angles.
  • FIGS. 16(A)-(C) an example electrochromic device with ECP-black and green colloidal crystal as two color layers is adopted again to assess the impacts of the surrounding light on this angle-dependent light variation are shown by the images taken under strong front surrounding light (on the same side of the viewing side) in FIGS. 16(A)-(C) and strong backlight (on the opposite side of the viewing side) in FIGS. 16(D)-(F).
  • the viewing angles are 0 °, 45 °, 70 0 from left to right.
  • FIG. 16(A) with the strong front surrounding light on the same side of viewing side, strong reflective intensity is observed and reflected light dominates in the perceived light.
  • FIGS. 16(A)-(C) show angle-dependent light variation among different angles. In contrast, with the strong back surrounding light on the opposite side of viewing side, strong transmittance intensity is observed, and transmitted light dominates in the perceived light. Since the transmittance intensity is not angle-dependent, insignificantly color change could be seen at any angles as shown in FIGS. 16(D)-(F), thus there is no clearly angle-dependent light variation.
  • the electrochromic device in the present disclosure show camouflage capability with angle-dependent light variation, which is realized through dedicatedly angle control and electric filed tuning, so that the disclosed electrochromic device can selectively express colors according to its position to the information receiver.
  • the camouflage capability is further demonstrated by the example electrochromic devices with an octopus pattern (as shown in FIGS. 17(A)-(B)) and an butterfly pattern (as shown in FIGS. 18(A)-(C)).
  • the example electrochromic devices incorporate both ECP-black and green colloidal crystal as two color layers. Before the device assembling, the colloidal crystals are printed into the desirable pattern with the help of UV light and photo mask. Then the colloidal crystals are crosslinked under UV light and then be transferred out after opening the glass and washed away the remaining liquid using ethyl glycol solvent.
  • the solidified colloidal crystals are sandwiched between two coated electrodes (ECP-black on the working electrode, ion storage layer on the counter electrode) with extra liquid electrolyte filled in between as well and followed by UV crosslinking again to finish the assembly. Since the compartments form the electrochromic device are flexible, the entire device can be cut into any shape as desired and wearable. As shown in FIG. 17(A), this device mounted on the arm of toy bear shows an octopus shape at a colored state. While with a positive voltage, the ECP- black becomes transparent and the octopus disappears as shown in FIG. 17(B). This show-hide process is reversible with the voltage switching. Similarly, a butterfly-shaped device in flowers can show (as FIG.
  • any desired patterned devices can be prepared to mimic the animals in nature, and with the electric filed tuning, the platform can easily realize the camouflage by becoming transparent, or mimicking the surrounding color and even producing angle dependent colors.
  • the color coupling endows the device with broader color gamut which enhances the color expression and the electric tunable angle-dependent light variation further facilitate the potential camouflage applications.
  • multiplex devices can also be prepared with patterned electrode/substrate.
  • FIG. 19(A) shows a scheme of a three-by-three array of multiplex device where each circle represents one electric tunable active area.
  • the patterned electrodes are respectively connected to power source (shown by the “+” and
  • FIG. 19(B) shows the final device can be bendable which eventually lead to angle diversity within the same multiplex device under single electric-field control.
  • the multiplex device can also be electrically tuned by various selective actuation. The angle-dependent light variation of the disclosure as well as its electric tunability can produce even more versatile colors on the multiplex device.
  • 19(C)- (F) show images of the three-by-three array multiplex device before (left) and after (right) selectively actuated with multiplied electric fields. These multiplex devices can be used for high- resolution display and camouflage pattern construction after computational programming.
  • the method to prepare multiplex devices further comprises a modification process to the substrate before assembling the device.
  • the ITO glass or PET-ITO substrates are glued with patterned parallel stripe tapes which have an interval of 2 cm to each other and then are immersed in the 10% HCL solution for 10 minutes. Then the substrates are taken out and washed by DI water for 3 times to remove HCL. Patterned parallel tapes are then peeled off to get patterned ITO substrates.

Abstract

L'invention concerne un dispositif électrochrome ayant une couche colorée pigmentaire et une couche colorée structurale. La couche colorée pigmentaire comprend des matériaux électrochromes, qui permettent des passages réversibles et graduels entre un état coloré et un état blanchi par un champ électrique. Dans un état coloré, le dispositif électrochrome présente une couleur additive structurale-pigmentaire saturée. Dans un état blanchi, la couleur structurale a disparu graduellement et conduit à l'état transmissif optique. Le couplage de couleur entre ces deux couches colorées fournit aux dispositifs selon l'invention une plus large gamme de couleurs et une plus large réponse optique dépendant de l'angle. Des dispositifs multiplexés et à motifs ont été en outre fabriqués pour démontrer les potentiels de camouflage biomimétique.
PCT/US2020/035407 2020-05-29 2020-05-29 Dispositif électrochrome basé sur deux couches colorées et procédés de fabrication de celui-ci WO2021242267A1 (fr)

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PCT/US2020/035407 WO2021242267A1 (fr) 2020-05-29 2020-05-29 Dispositif électrochrome basé sur deux couches colorées et procédés de fabrication de celui-ci
CN202080076632.XA CN114787707B (zh) 2020-05-29 2020-05-29 基于两个色层的电致变色器件及其制备方法
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US11874578B2 (en) 2022-02-09 2024-01-16 Ambilight Inc. High transparency electrochromic polymers
US11879098B2 (en) 2022-02-09 2024-01-23 Ambilight Inc. High transparency electrochromic polymers

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CN114787707A (zh) 2022-07-22
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